Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
  • C08G59/5033—Amines aromatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

• Epoxide resin/curing agent systems which can be used for producing fibre-reinforced plastics, such as laminates, are known. It is of advantage for impregnating the fibres when these systems are liquid and of low viscosity, and for this reason the systems contain liquid acid anhydrides as curing agents. After prolonged contact with water, cured composites produced from a system of this type commence to decompose as a result of hydrolysis, a disadvantage which, as is known, epoxide resin systems with aromatic amine curing agents do not have. Systems of this kind, however, are solid and/or cure only at very high temperatures. The curing temperature can indeed be lowered by the addition of accelerators, but there is a simultaneous shortening of the pot life, so that such systems are not suitable for carrying out filament winding or pultrusion on an industrial scale.
• the invention relates therefore to a liquid matrix system, based on a mixture of epoxide resin and an amine curing agent for the epoxide resin, for producing fibre-reinforced plastics components, which system is characterised in that it has at 40° C. a dynamic viscosity of less than 400 mPa s, preferably less than 250 mPa s, and contains
• Polyglycidyl compounds (a) are preferably those based on bisphenol-F or on bisphenol-A, or based on phenolnovolaks, or on mixtures thereof in any mixture ratio. They can be mixed with a polyglycide of an alkanediol, such as butanediol diglycide, preferably in an amount of 3-5 percent by weight, relative to the total amount of the polyglycidyl compounds, or with an aromatic compound having amino and hydroxyl groups, such as diglycidyl-p-aminophenol, preferably in an amount of 3-20 percent by weight, relative to the total amount of polyglycidyl compounds.
• an alkanediol such as butanediol diglycide
• an aromatic compound having amino and hydroxyl groups such as diglycidyl-p-aminophenol
• polyglycidyl compounds are triglycidyl-p-aminophenol and tetraglycidyl-p,p'-diaminodiphenylmethane, which can be mixed with butanediol diglycide or triglycidyl-p-aminophenol.
• the compounds mentioned can also be used in any admixtures with one another or with hydantoin diglycidyl compounds, such as N,N'-diglycidyl-5,5-dimethylhydantoin, provided that the viscosity of the final mixture at 40° C. is less then 400 mPa s.
• the accelerator (c) is advantageously mixed with diethyltoluylenediamine (mostly 1-methyl-3,5-diethyl-2,4-diaminobenzene, but also 1-methyl-3,5-diethyl-2,6-diaminobenzene) in a quantitative ratio within the stated range.
• Suitable accelerators are tertiary amines, for example 1-methyl-imidazole, or phenols, such as salicylic acid, especially however borofluoroamine complexes of organic compounds, such as BF 2 -acetoacetanilide, BF 3 -aniline complexes or BF 3 -monoethylamine.
• the component (b) having at all events to be present to the extent of at least 50 percent by weight in the mixture (b)+(c)+(d).
• the matrix system according to the invention is preferably applied without solvent. It can however contain, relative to the total weight of the matrix system, up to 20% of an inert solvent, such as toluene, also up to 20% of a reactive vinyl or acrylic polymer with the corresponding radical initiators, up to 5% of an adhesion promoter and up to 2% of a dye.
• an inert solvent such as toluene
• a reactive vinyl or acrylic polymer with the corresponding radical initiators up to 5% of an adhesion promoter and up to 2% of a dye.
• the matrix system according to the invention preferably contains a mixture of diglycidyl ether of bisphenol-F and bisphenol-A, the epoxide content being 5.3-6.1 val/kg, and, relative to the total amount of glycidyl compounds, 3-15 percent by weight of diglycidyloxybutane or 3-20 percent by weight of triglycidyl-p-aminophenol, as well as (b) a mixture of 95-98 percent by weight of diethyltoluylenediamine and 2-5 percent by weight of BF 2 -acetoacetanilide.
• This mixture preferably has at 40° C. a dynamic viscosity of less than 250 mPa s.
• a matrix system which contains as component (a) a mixture of 65 percent by weight of diglycidyl ether of bisphenol-F (epoxide content: 5.8-6.1 val/kg), 30 percent by weight of diglycidyl ether of bisphenol-A (epoxide content: 5.3-6.7 val/kg) and 5 percent by weight of diglycidyloxybutane (epoxide content: 8.5-9.5 val/kg), and, as components (b) and (c), a mixture of 96 percent by weight of diethyltoluylenediamine and 4 percent by weight of difluoroboroacetoacetanilide.
• component (a) a mixture of 65 percent by weight of diglycidyl ether of bisphenol-F (epoxide content: 5.8-6.1 val/kg), 30 percent by weight of diglycidyl ether of bisphenol-A (epoxide content: 5.3-6.7 val/kg) and 5 percent by weight of diglycidyloxybutan
• the matrix according to the invention is used to produce fibre-reinforced plastics. It is thus possible, using known impregnating methods, to impregnate and cure fibre materials such as filaments, rovings, mats or fabrics. Advantageous factors in the procedure are the low viscosity at the working temperatures (at 40°-60° C.), the long pot life and the short gelling and curing times.
• the cured components have good mechanical strengths, high glass transition temperatures and very high thermal stability. Furthermore, their stability in water and resistance to chemicals, particularly at elevated temperatures and after prolonged periods of time, are better than in the case of resin/anhydride curing agent systems, which likewise are systems having low viscosity.
• the matrix of the invention is suitable for producing prepegs, especially where the operations are performed without solvents, and for use in the pultrusion process, in which the procedure can be carried out with or without solvents; in addition, the matrix is particularly advantageous in those technical fields of operation where solvents have to be avoided, such as in the case of injection moulding or in particular filament winding for producing high-strength, thermally and chemically resistant structural components in large-scale series production.
• the matrix according to the invention can be employed for example for manufacturing hollow objects, for instance tubes capable of withstanding pressure and torsional stress, such as tubes for universal-joint shafts, stabilisers and axles, and also for producing fibre-reinforced solid materials, for example spring elements.
• the process for producing fibre-reinforced plastics components which process comprises using the matrix system for impregnating fibre material, forming shaped articles by filament winding or pultrusion and subsequently heating the shaped components at 100°-180° C., especially at 100°-140° C., is likewise subject matter of the present invention.
• Suitable fibre materials are preferably glass fibres, for example those formed from E- or S-glass, aramid fibres, high-modulus and high-strength carbon fibres made from polyacrylonitrile or pitch, and also polyester and polyamide fibres.
• the content of fibre material in the cured final product varies depending on the method of production and on the nature of the fibres, for example in a product formed by filament winding the content is between 45 and 75 percent by volume.
• filament winding precision winding
• precision winding an operation whereby prestretched, parallel running fibres, impregnated in a resin/curing agent system, are wound round a mandrel, the fibres being located according to a precisely predetermined geometrical pattern.
• the pultrusion process has similar features. In this case, however, the impregnated rovings are shaped by being pulled through a heated dye and pre-cured to the extent that subsequent curing in a through-type oven can no longer lead to deformation or delamination.
• a matrix system having a dynamic viscosity of 220 mPa s at 40° C. is thus obtained.
• the product has a glass transition temperature (T G ) of 168° C. after curing for 8 hours at 140° C., and a T G of 169° C. after curing for 4 hours at 180° C.
• the matrix system is used for impregnating fibres made from glass, carbon and aramid, from which are produced, by the filament winding process, unidirectional specimens which are subjected, according to W. Knappe and W. Schneider: "Rupture criteria for unidirectional glass-fibre plastics under plane short- and long-duration stressing" in Kunststoffe (Plastics) 62, No. 12, 1972, to the tensile, compression and torsion tests.
• 75 parts by weight of polyglycidyl ether of epoxyphenol novolak (epoxide content: 5.7 val/kg) and 25 parts by weight of 1,4-butanediol-diglycidyl ether (epoxide content: 9.2 val/kg) are homogeneously mixed together.
• Into the mixture are stirred 30 parts by weight of a mixture of 83 parts by weight of 1-methyl-3,5-diethyl-2,4-diaminobenzene and 13 parts by weight of p,p'-diamino-diphenylmethane and 4 parts by weight of BF 2 -acetoacetanilide.
• T G glass transition temperature
• the tensile strength determined perpendicularly to the fibres on wound objects reinforced unidirectionally with 65% v/v of glass fibres "Cosmostrand 859 ⁇ 29/890"® is 54 N/mm 2 .
• the matrix system obtained has at 50° C. a dynamic viscosity of 193 mPa s.
• the product has a T G of 178° C. after a curing time of 8 hours at 140° C.
• the boiling-water absorption, according to ISO R 117, after 1 hour is 0.24%.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
• Reinforced Plastic Materials (AREA)
• Epoxy Resins (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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Cited By (20)

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• 1981
  • 1981-07-16 US US06/283,766 patent/US4366108A/en not_active Expired - Fee Related
  • 1981-07-22 DE DE19813129016 patent/DE3129016A1/de not_active Ceased
  • 1981-07-22 GB GB8122650A patent/GB2093034B/en not_active Expired
  • 1981-07-24 CA CA000382473A patent/CA1175196A/fr not_active Expired
  • 1981-07-24 FR FR8114399A patent/FR2487371B1/fr not_active Expired
  • 1981-07-25 JP JP56117013A patent/JPS5751719A/ja active Pending

Patent Citations (2)

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